US20120156377A1 - Agent for treating hard surfaces - Google Patents

Agent for treating hard surfaces Download PDF

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Publication number
US20120156377A1
US20120156377A1 US13/409,354 US201213409354A US2012156377A1 US 20120156377 A1 US20120156377 A1 US 20120156377A1 US 201213409354 A US201213409354 A US 201213409354A US 2012156377 A1 US2012156377 A1 US 2012156377A1
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alkyl
agent
agent according
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Inventor
Birgit VEITH
Mirko Weide
Nadine Warkotsch
Brigitte Giesen
Stefan Stumpe
Roland Breves
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Assigned to HENKEL AG & CO. KGAA reassignment HENKEL AG & CO. KGAA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: STUMPE, STEFAN, WARKOSTCH, NADINE, WEIDE, MIRKO, BREVES, ROLAND, VEITH, BIRGIT, GIESEN, BRIGITTE
Publication of US20120156377A1 publication Critical patent/US20120156377A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3738—Alkoxylated silicones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention generally relates to agents used in treating a hard surface, and more particularly relates to agents used for cleaning and/or providing a dirt-repellent finish on hard surfaces.
  • agents have also been found with which surfaces may subsequently be provided with a finish in a manner which can be carried out domestically such that, at least for a certain service life, they are less easily soiled or may be cleaned more easily (also known as a “semi-permanent finish”).
  • Patent application WO 2006/005358 discloses copolymers which consist of at least one of each of an anionic vinyl monomer, a vinyl monomer with a quaternary ammonium group or a tertiary amino group, and a nonionic hydrophilic vinyl monomer or a polyfunctional vinyl monomer. These copolymers are suitable as soil-inhibiting components in cleaning agents and are effective, for example, against fecal soiling.
  • a further problem may also arise from the fact that, to enhance dissolution of lime, toilet cleaning agents are not uncommonly left to act on the ceramics for an extended period of time, often for several hours or even overnight.
  • the formulations are generally thickened.
  • a film then forms on the surface which, due to the product color, is usually colored and, once having dried on, can only be removed with difficulty.
  • Biofilms consist of a mucilaginous layer (film) in which microorganisms (for example bacteria, algae, fungi, protozoa) are embedded. This may constitute a problem of not only a hygienic but also an esthetic nature. Biocidal substances are frequently used as countermeasures. However, this is not always without its own problems due to the ecotoxicological properties of many of these substances and the associated restrictions on their use. Moreover, biofilms contribute to the formation of unpleasant smelling substances and are therefore a source of unwanted malodors, in particular in sanitary applications.
  • microorganisms for example bacteria, algae, fungi, protozoa
  • Agents for treating hard surfaces must furthermore satisfy other requirements. For instance, it is important for the appearance of the surface not to be impaired after it has been treated. Factors which are in particular of importance here are the retention of gloss on surfaces which in the original or clean state are glossy and the avoidance of residues of the treatment agent, for example in the form of lines or streaks.
  • PCT Application Publications WO 2008/068236 and WO 2008/068235 disclose the use of multi-armed silyl polyalkoxylates for providing a finish on surfaces. Also, PCT Application Publication WO 2009/071452 discloses that polyesteramides may be used to provide a finish on surfaces.
  • an agent for treating a hard surface, in particular for cleaning and/or for providing a dirt-repellent finish on a hard surface and/or for reducing the adhesion of microorganisms to a hard surface, where said agent comprises at least two components selected from the group consisting of: (a) a multi-armed stellate polyalkoxylate; (b) a polyesteramide; and (c) a copolymer prepared from a quaternary ammonium acrylamide and acrylic acid.
  • the agent for treating hard surfaces comprises a mixture of a multi-armed silyl polyalkoxylate and a polyesteramide.
  • a mixture of a multi-armed silyl polyalkoxylate and a copolymer prepared from a quaternary ammonium acrylamide and acrylic acid is used.
  • a mixture of a polyesteramide and a copolymer prepared from a quaternary ammonium acrylamide and acrylic acid is used.
  • a mixture of a multi-armed silyl polyalkoxylate, a polyesteramide and a copolymer prepared from a quaternary ammonium acrylamide and acrylic acid is used.
  • the present invention is an agent is for treating a hard surface, in particular for cleaning and/or for providing a dirt-repellent finish on a hard surface and/or for reducing the adhesion of microorganisms to a hard surface, comprising at least two components selected from the group consisting of: (a) a multi-armed stellate polyalkoxylate; (b) a polyesteramide; and (c) a copolymer prepared from a quaternary ammonium acrylamide and acrylic acid.
  • Multi-armed stellate polyalkoxylates for the purposes of the present invention contain polymer arms which are attached in substantially stellate or radial manner to a central unit and in each case comprise polyoxyalkylene units, preferably polyoxyethylene units and/or polyoxypropylene units.
  • the number of polymer arms preferably amounts to 3 to 20, in particular to 3 to 8.
  • the mass-average (weight-average) molecular weight preferably amounts to 500 to 100,000, in particular to 1,000 to 50,000, and particularly preferably to 2,000 to 30,000.
  • Functional groups such as for instance positively or negatively charged groups or reactive groups may optionally be located peripherally on the polymer arms.
  • Multi-armed stellate polyalkoxylates which may be used according to the invention are described for example in patents WO 2003/063926, WO 2007/096056 and DE102008063070.
  • the multi-armed stellate polyalkoxylate is a silyl polyalkoxylate or a mixture of a plurality of these compounds, in which the silyl group is preferably located peripherally on the polymer arms.
  • the silyl polyalkoxylate here preferably contains 0.3 to 10 wt. %, particularly preferably 0.5 to 5 wt. % of silicon, relative to the total weight of the silyl polyalkoxylate.
  • Alkoxy and alkyl groups are preferably attached to the peripheral silyl groups themselves; instead or in addition, further functional groups may in turn be attached to the silyl groups.
  • the multi-armed silyl polyalkoxylate preferably comprises a compound of the formula (I):
  • Z denotes an (o+p)-valent residue with at least three carbon atoms
  • D denotes a divalent polyoxyalkylene residue in which the o+p polyoxyalkylene residues attached to Z may differ from one another and one residue D is in each case joined to Z via an oxygen atom belonging to Z and an oxygen atom belonging to D is joined to E or hydrogen
  • E denotes a chemical bond or a divalent organic residue with 1 to 50 carbon atoms
  • OR 1 denotes a hydrolyzable group
  • R 1 and R 2 mutually independently denote a linear or branched alkyl group with 1 to 6 carbon atoms
  • r denotes an integer from 1 to 3
  • p denotes 0 or an integer ⁇ 1, and o+p has a value of 3 to 100.
  • Z preferably denotes an at least trivalent, in particular tri- to octavalent, acyclic or cyclic hydrocarbon residue with 3 to 12 carbon atoms, in which the residue may be saturated or unsaturated and in particular also aromatic.
  • Z particularly preferably denotes the trivalent residue of glycerol or the tri- to octavalent residue of a sugar, for example the hexavalent residue of sorbitol or the octavalent residue of sucrose.
  • the x-valent residue of one of the above-stated polyols should here be taken to mean the molecular fragment of the polyol which remains after removal of the hydrogen atoms from x alcoholic or phenolic hydroxyl groups.
  • Z may in principle denote any central unit which is known from the literature for producing stellate (pre)polymers.
  • D preferably denotes groups selected from poly-C 2 -C 4 -alkylene oxides, particularly preferably a (co)polymer of ethylene oxide and/or propylene oxide, in particular a copolymer with a proportion of propylene oxide of up to 60 wt. %, preferably of up to 30 wt. % and particularly preferably of up to 20 wt. %, in which the polymers may be random and/or block copolymers.
  • poly-C 2 -C 4 -alkylene oxides particularly preferably a (co)polymer of ethylene oxide and/or propylene oxide, in particular a copolymer with a proportion of propylene oxide of up to 60 wt. %, preferably of up to 30 wt. % and particularly preferably of up to 20 wt. %, in which the polymers may be random and/or block copolymers.
  • D in the formula (I) denotes —(CHR 3 —CHR 4 —O) q —, in which R 3 and R 4 mutually independently mean hydrogen, methyl or ethyl and q means an integer from 2 to 10,000.
  • E in particular denotes a chemical bond or a divalent, low molecular weight organic residue with preferably 1 to 50, in particular 2 to 20 carbon atoms.
  • divalent low molecular weight organic residues are short-chain aliphatic and heteroaliphatic residues such as for example —(CH 2 ) 2 —, —(CH 2 ) 3 —, —C(O)—NH—(CH 2 ) 3 -und —C(O)—NH—X—NH—C(O)—NH—(CH 2 ) 3 —, in which X denotes a divalent aromatic residue such as the phenylene residue or denotes an alkylidene residue.
  • E very particularly preferably denotes a bond or the residue —C(O)—NH—(CH 2 ) 3 —.
  • R 1 and R 2 mutually independently denote methyl or ethyl, and R denotes 2 or 3.
  • residues —Si(OR 1 ) r (R 2 ) 3 are dimethylethoxysilyl, dimethylmethoxysilyl, diisopropylethoxysilyl, methyl dimethoxysilyl, methyldiethoxysilyl, trimethoxysilyl, triethoxysilyl or tri-t-butoxysilyl residues, but trimethoxysilyl and triethoxysilyl residues are very particularly preferred.
  • R 1 and R 2 are identical and to denote methyl or ethyl.
  • r denote the number 3.
  • the total of o+p preferably amounts to 3 to 50, in particular 3 to 10 and particularly preferably 3 to 8, and matches the number of arms which are attached to the central unit Z in the compound (I).
  • the central unit therefore preferably has 3 to 50, in particular 3 to 10 and particularly preferably 3 to 8 oxygen atoms which serve as connection points for the arms.
  • o is equal to 0.
  • the ratio o:p is between 99:1 and 1:99, preferably 49:1 and 1:49, and in particular 9:1 and 1:9.
  • the agent contains a mixture of at least two, in particular two to four different multi-armed silyl polyalkoxylates of the formula (I).
  • At least two different multi-armed silyl polyalkoxylates are particularly preferred here for the at least two different multi-armed silyl polyalkoxylates to differ in their number of arms.
  • a first silyl polyalkoxylate with 3 to 6 arms is here advantageously combined with a second silyl polyalkoxylate with 6 to 10 arms.
  • two different multi-armed silyl polyalkoxylates are used, they are generally present in a quantity ratio of 99:1 to 1:99, preferably of 49:1 to 1:49, and in particular of 9:1 to 1:9.
  • silyl polyalkoxylates usable according to the invention With regard to the production of silyl polyalkoxylates usable according to the invention, reference is in particular also made to published patent applications WO 2008/068236 and WO 2008/068235.
  • Suitable polyalkoxylate precursors for producing silyl polyalkoxylates usable according to the invention are obtainable for example under the trade names Voranol 4053, Wanol R420 or Voranol CP 1421.
  • Voranol 4053 is a polyether polyol (poly(ethylene oxide-co-propylene oxide)) from DOW Chemicals.
  • the arms are random copolymers of approx. 75% EO and approx. 25% PO, the OH functionality (hydroxyl end groups) amounts on average to 6.9 at a mass-average (weight-average) molecular weight of approx. 12,000. This results in a ratio of approx. 78% octa-armed polyether polyol and approx. 22% tri-armed polyether polyol.
  • Wanol R420 from WANHUA, China, which is a mixture of a linear poly(propylene/ethylene)diethylene glycol and an octa-armed polyether polyol (poly(propyleneoxy/ethyleneoxy)sucrose) in a ratio of approx. 15-25:85-75.
  • Another commercially obtainable polyether polyol is Voranol CP 1421 from DOW Chemicals, which comprises a tri-armed random poly(ethylene oxide-co-propylene oxide) with an EO:PO ratio of approx. 75:25 and a mass-average (weight-average) molecular weight of approx. 5000.
  • silyl polyalkoxylates usable according to the invention are obtainable from these polyalkoxylate precursors by reacting the hydroxyl end groups of these multi-armed polyalkoxylate precursors with functional silanes which comprise a functional group which is reactive towards the hydroxyl end groups of the polyalkoxylate precursors.
  • Examples are tetraalkoxysilanes such as tetramethyl silicate and tetraethyl silicate, (meth)acrylate silanes such as (3-methacryloxypropyl)trimethoxysilane, (methacryloxymethyl)triethoxysilane, (methacryloxymethyl)methyldimethoxysilane and (3-acryloxypropyl)trimethoxysilane, isocyanatosilanes such as (3-isocyanatopropyl)trimethoxysilane, (3-isocyanatopropyl)triethoxysilane, (isocyanatomethyl)methyldimethoxysilane and (isocyanatomethyl)trimethoxysilane, aldehyde silanes such as triethoxysilylundecanal and triethoxysilylbutyraldehyde, epoxy silanes such as (3-glycidoxypropyl)-trimethoxysilane,
  • Silyl polyalkoxylates usable according to the invention are particularly preferably produced using tetraalkoxysilanes, isocyanatosilanes or anhydride silanes, but in particular isocyanatosilanes or anhydride silanes.
  • the multi-armed, stellate polyalkoxylate, and in particular the silyl polyalkoxylate, is used in the agents according to the invention preferably in a quantity of 0.001 to 5 wt. %, in particular of 0.005 to 2 wt. %, particularly preferably of 0.02 to 0.5 wt. % and above all of 0.05 to 0.3 wt. %, in each case relative to the total weight of the agent.
  • polyesteramides to be used according to the invention preferably contain at least two groups according to the formula (II):
  • Y denotes H, C 1-20 alkyl, C 6-10 aryl
  • B denotes C 2-24 alkylene or C 6-24 arylene
  • R1, R2, R3, R4, R5 and R6 mutually independently denote H, C 1-8 alkyl or C 6-10 aryl
  • R7 and R8 mutually independently denote C 1-28 alkyl or C 6-10 aryl optionally substituted by heteroatoms
  • m and n mutually independently assume a value from 1 to 4, in which the value of m and n preferably amounts to 1.
  • the polyesteramide here particularly preferably comprises a polymer according to formula (IV):
  • W denotes H, C 1-20 alkyl, C 6-10 aryl or
  • A denotes OH or
  • B denotes C 2-24 alkylene or C 6-24 arylene
  • X 1 denotes
  • X 2 denotes H, X 1
  • R1, R2, R3, R4, R5 and R6 mutually independently denote H, C 1-8 alkyl, C 6-10 aryl or —CH 2 —OX 2 ; and R7 and R8 mutually independently denote C 1-28 alkyl or C 6-10 aryl optionally substituted by heteroatoms or by groups containing heteroatoms.
  • the polyesteramide is a polymer according to formula (V):
  • B denotes C 2-24 alkylene or C 6-24 arylene
  • X 1 denotes
  • X 2 denotes hydrogen
  • R3 and R6 mutually independently denote H, C 1-8 alkyl or C 6-10 aryl; and R7 and R8 mutually independently denote C 1-28 alkyl or C 6-10 aryl optionally substituted by heteroatoms or by groups containing heteroatoms.
  • R3 and R6 preferably denote C 1-4 alkyl, particularly preferably methyl or ethyl.
  • R7 and R8 preferably denote C 1-20 alkyl optionally substituted by heteroatoms and/or by groups containing heteroatoms, particularly preferably C 2 , C 3 or C 6 alkyl substituted by heteroatoms and/or by groups containing heteroatoms.
  • R7 and R8 may in particular be mono- or polysubstituted by groups selected from alcohols, ethers, polyethers, esters, cyanide, carbonate, urethane, urea, amide, imide, amine, imine, imidazole, oxime, sulfide, thiol, thiourea, sulfone, sulfone oxide, sulfate, phosphate, phosphine, phosphine oxide, silane, silicone, silicate, fluorine, chlorine, bromine or iodine and from groups which contain at least one of the above-stated functional groups.
  • residues R7 and R8 include di(m)ethylaminoethyl, di(m)ethylaminopropyl and di(m)ethylaminohexyl and quaternized forms of these residues; tri(m)ethylsilylpropyl, tri(m)ethoxysilylpropyl, perfluoroctyl, perfluoroctyl(m)ethyl, (m)ethoxyethyl, (m)ethoxy-2-propyl, maleimidopropyl, maleimidohexyl, octenylsuccinimidohexyl, hexahydrophthalimidohexyl, 2-(benzo)imidazolethyl, diphenylphosphinoethyl, furfuryl, cyanoethyl, cyanopropyl and optionally substituted morpholine, thiomorpholinyl,
  • the residues R7 and R8 mutually independently contain quaternized amino groups or polyether groups, in particular polyoxyethylene groups, or any desired mixtures thereof, in which in the same molecule some residues R7 and R8 may contain only quaternized amino groups and other residues R7 and R8 only polyether groups, in particular polyoxyethylene groups.
  • the polyoxyethylene groups here preferably contain 3 to 20, particularly preferably 5 to 15, in particular 6 to 10 oxyethylene units, in which the hydroxyl end group of the oxyethylene units may be etherified with a short-chain alcohol, in particular methanol.
  • At least 10%, preferably at least 20% or 30%, of the residues R7 and R8 are tri(m)ethylammonium alkyl residues, in particular selected from tri(m)ethylammonium ethyl, tri(m)ethylammonium propyl and tri(m)ethylammonium hexyl.
  • At least 10%, preferably at least 20% or 30%, of the residues R7 and R8 are polyoxyethylene groups with 6 to 10, preferably with 7, 8 or 9, oxyethylene units, which may optionally be terminally etherified with methyl or ethyl.
  • B may optionally be substituted, preferably by a C 1-26 alkyl residue, particularly preferably by methyl, octenyl, nonenyl, decenyl, undecenyl or dodecenyl.
  • B may here in particular be a residue optionally substituted by one of the above-stated residues selected from ethylene, ethenylene, 1,3-propylene, 1,2-cyclohexyl, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,3-norbornyl, 2,3-norbornen-5-yl and 1,2-cyclohex-4-enyl.
  • the molecular weight of the polyesteramides according to the invention preferably amounts to from 600 g/mol to 50,000 g/mol, particularly preferably from 1,000 g/mol to 40,000 g/mol, above all from 5,000 g/mol to 35,000 g/mol.
  • the polyesteramide according to the invention may be both linear and branched, but is preferably a branched polymer, particularly preferably a highly branched polymer.
  • Polyesteramides which are usable according to the invention are for example obtainable under the trade names Hybrane DAEO 5000 28037 or Hybrane Quat 48 from DSM.
  • polyesteramides are present in the agents according to the invention preferably in a quantity of 0.02 to 5.0 wt. %, particularly preferably in a quantity of 0.05 to 2.0 wt. %, in particular in a quantity of 0.1 to 1.0 wt. %, above all in a quantity of 0.1 to 0.8 wt. %.
  • copolymers prepared from a quaternary ammonium acrylamide and acrylic acid are preferably copolymers prepared from diallyldimethylammonium acrylamide and acrylic acid.
  • Such copolymers are for example obtainable under the trade name Mirapol Surf from Rhodia. Mirapol Surf-S100, Mirapol Surf-S110, Mirapol Surf-S210 or Mirapol Surf-S500 and mixtures thereof may above all be used according to the invention.
  • copolymers prepared from a quaternary ammonium acrylamide and acrylic acid are present in the agents according to the invention preferably in a quantity of 0.1 to 5.0 wt. %, particularly preferably in a quantity of 0.2 to 2.0 wt. %, in particular in a quantity of 0.3 to 1.0 wt. %, above all in a quantity of 0.4 to 0.8 wt. %.
  • hard surfaces in particular comprise surfaces of stone or ceramic materials, rigid plastics materials, glass or metal.
  • Hard surfaces may be, for example, walls, work surfaces, flooring or sanitary articles.
  • the invention relates to surfaces of ceramics, preferably ceramic sanitary ware, and very particularly of toilet bowls.
  • Embodiments of the present invention encompass any presentations of the agents according to the invention which are established in the prior art and/or are convenient. These include for example solid, pulverulent, liquid, gel-form or pasty agents, optionally also comprising two or more phases, compressed or uncompressed; they furthermore include extrudates, granules, tablets or pouches, packaged both in large containers and in portions.
  • the agent according to the invention is preferably a toilet cleaner, a bathroom cleaner or a multipurpose cleaner.
  • the agent according to the invention preferably has a pH value of 1 to 5, in particular of 1 to 3; when used as a bathroom cleaner it preferably has a pH value of 1 to 6, in particular of 3 to 5; and when used as a multipurpose cleaner it preferably has a pH value of 8 to 12, in particular of 9 to 11.
  • Methods suitable for treating a surface are any conventional methods with which the agent may be applied onto the surface.
  • the surface is preferably treated by the agent being transferred onto the surface with the assistance of an absorbent fabric or by the agent being sprayed onto the surface.
  • treatment may, for example, also proceed by immersing the surface in the agent.
  • dirt or soiling should in particular be taken to mean fecal soiling and/or biofilms.
  • Treating a hard surface with the agent according to the invention protects it from soiling and/or facilitates the detachment of soiling from the surface and/or reduces the adhesion of microorganisms.
  • “Reducing adhesion” should here preferably be taken to mean that at least 20, 40 or 60%, particularly preferably at least 80, 90 or 95% fewer microorganisms adhere to the hard surface than when a treatment agent without the addition of polymers to be used according to the invention is used. The percentages here relate to the difference in the total mass of the adhered material.
  • microorganisms are preferably selected from bacteria, fungi, in particular molds, viruses, in particular bacteriophages, and algae.
  • the bacteria, the adhesion of which is reduced are preferably selected from the group consisting of Gram-negative and Gram-positive bacteria, above all pathogenic bacteria selected from Propionibacterium acnes, Staphylococcus aureus, Streptococcus spp., Corynebacterium spp., Micrococcus spp. (in particular M. sedentarius ), Bacillus anthracia, Neisseria spp., Pseudomonas aeruginosa, P.
  • Microorganisms which are of particular relevance with regard to biofilm formation, and the adhesion of which is particularly preferably reduced, are for example aeromonads, Agrobacterium, Aquabacterium, Bradyrhizobium japonicum, Burkholderia cepacia, Chromobacterium violaceum , Dermacocci, Enterobacter agglomerans, Erwinia carotovora, Erwinia chrysanthemi, Escherichia coli, Nitrosomona europaea, Obesumbacterium proteus, Pantoea stewartii , pseudomonads, Ralstonia solanacearum, Rhizobium, Rhodobacter sphaeroides, Salmonella enterica, Serratia, Vibrio anguillarum, Vibrio fischeri, Xanthomonas, Xenorhabdus nematophilus, Yersinia, Zooshikella gangwhensis, Cythophaga sp.
  • biofilm formers are also of relevance in the maritime sector, since they may be partly responsible for “fouling” on submerged surfaces.
  • the agent preferably prevents the formation of biofilms. It is suspected that the efficacy of the agents used according to the invention against the formation of biofilms is attributable to a bacteriostatic action of the polymers used, whereby colonization of the surfaces with microorganisms is inhibited and their adhesion and multiplication on the surfaces is prevented. On the other hand, since no biocidal effects have been observed for the agents, they do not suffer from the above-mentioned disadvantages of using biocides.
  • the agents according to the invention bring about easier removability of soiling and a reduction in susceptibility to resoiling and in particular improve the cleaning performance of cleaning agents for hard surfaces. As a result, surfaces treated or cleaned accordingly are perceived to be clean for longer.
  • polymer mixtures according to the invention as an additive in surfactant-containing cleaning agents makes it possible in a single step not only to clean a surface, but also simultaneously to provide it with protection from dirt. In this manner, lime deposition, adhesion of dirt containing protein or fat and also bacterial growth are, for example, prevented. The treated surfaces stay clean longer and subsequent cleaning is furthermore considerably facilitated. This means that, without any negative impact on cleanness, the surfaces need be cleaned less often, and subsequent cleaning thereof is associated with less effort in that it can proceed more quickly and/or requires gentler cleaning agents. In favorable cases, it is thus possible to achieve an adequate cleaning action for a certain time just with water, i.e. without requiring the use of a conventional cleaning agent.
  • the polymers of the polymer mixtures according to the invention may straightforwardly and simply be formulated together with the other components of the agent and may in particular also very simply be incorporated into conventional cleaning agent formulations.
  • the advantageous solubility characteristics of these substances mean that incorporating them into conventional cleaning agents does not result in any limitations, such as for instance impaired sprayability.
  • the agent according to the invention furthermore contains at least one hydrolyzable silicic acid derivative.
  • Hydrolyzable silicic acid derivatives should in particular be taken to mean the esters of orthosilicic acid, in particular tetraalkoxysilanes and very particularly preferably tetraethoxysilane.
  • hydrolyzable silicic acid derivatives should, however, also be taken to mean compounds which, in addition to three alkoxy groups, also bear a carbon residue on the silicon atom, such as for example N-(triethoxysilylpropyl)-O-polyethylene oxide urethane, dimethyloctadecyl-(3-(trimethoxysilylpropyl)-ammonium chloride, diethylphosphatoethyltriethoxysilane and the trisodium salt of N-(trimethoxysilylpropyl)ethylendiaminetriacetic acid.
  • the further components present in the agents according to the invention should be selected in accordance with their nature and the quantity used such that no undesired interactions occur with the polymers to be used according to the invention.
  • the agents according to the invention contain at least one surfactant which is selected from anionic, nonionic, amphoteric and cationic surfactants and mixtures thereof.
  • surfactant which is selected from anionic, nonionic, amphoteric and cationic surfactants and mixtures thereof.
  • Anionic surfactants which are preferably suitable are C 8 -C 18 alkylbenzene sulfonates, in particular with around 12 C atoms in the alkyl moiety, C 8 -C 20 alkane sulfonates, C 8 -C 18 monoalkyl sulfates, C 8 -C 18 alkyl polyglycol ether sulfates with 2 to 6 ethylene oxide units (EO) in the ether moiety and sulfosuccinic acid mono- and di-C 8 -C 18 -alkyl esters.
  • C 8 -C 18 alkylbenzene sulfonates in particular with around 12 C atoms in the alkyl moiety
  • C 8 -C 20 alkane sulfonates C 8 -C 18 monoalkyl sulfates
  • C 8 -C 18 ⁇ -olefin sulfonates sulfonated C 8 -C 18 fatty acids, in particular dodecylbenzenesulfonate, C 8 -C 22 carboxylic acid amide ether sulfates, C 8 -C 18 alkyl polyglycol ether carboxylates, C 8 -C 18 N-acyl taurides, C 8 -C 18 —N-sarcosinates and C 8 -C 18 alkyl isethionates or mixtures thereof.
  • the anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of sulfonates, also in the form of their corresponding acid, for example dodecylbenzenesulfonic acid.
  • examples of such surfactants are sodium cocoalkyl sulfate, sodium sec.-alkanesulfonate with approx. 15 C atoms and sodium dioctylsulfosuccinate.
  • Sodium fatty alkyl sulfates and fatty alkyl+2EO ether sulfates with 12 to 14 C atoms have proved particularly suitable.
  • Nonionic surfactants which may primarily be mentioned are C 8 -C 18 alcohol polyglycol ethers, i.e. ethoxylated and/or propoxylated alcohols with 8 to 18 C atoms in the alkyl moiety and 2 to 15 ethylene oxide (EO) and/or propylene oxide (PO) units, C 8 -C 18 carboxylic acid polyglycol esters with 2 to 15 EU, for example tallow fatty acid+6 EO esters, ethoxylated fatty acid amides with 12 to 18 C atoms in the fatty acid moiety and 2 to 8 EO, long-chain amine oxides with 14 to 20 C atoms and long-chain alkyl polyglycosides with 8 to 14 C atoms in the alkyl moiety and 1 to 3 glycoside units.
  • C 8 -C 18 alcohol polyglycol ethers i.e. ethoxylated and/or propoxylated alcohols with 8 to 18 C atoms in the al
  • surfactants examples include oleyl-cetyl alcohol with 5 EO, nonylphenol with 10 EO, lauric acid diethanolamide, cocoalkyl dimethylamine oxide and cocoalkyl polyglucoside with on average 1.4 glucose units.
  • C 8-18 fatty alcohol polyglycol ethers with in particular 2 to 8 EO, for example C 12 fatty alcohol+7-EO ether, and C 8-10 alkyl polyglucosides with 1 to 2 glycoside units are particularly preferably used.
  • the nonionic surfactant is selected from the group comprising polyalkylene oxides, in particular alkoxylated primary alcohols, the polyalkylene oxides possibly also being end group-terminated, alkoxylated fatty acid alkyl esters, amine oxides and alkyl polyglycosides and mixtures thereof.
  • Sitable amphoteric surfactants are for example betaines of the formula (R iii )(R iv )(R v )N + CH 2 COO ⁇ , in which R iii means an alkyl residue with 8 to 25, preferably 10 to 21 carbon atoms optionally interrupted by heteroatoms or groups of heteroatoms and R iv and R v mean identical or different alkyl residues with 1 to 3 carbon atoms, in particular C 10 -C 18 alkyl dimethyl carboxymethyl betaine and C 11 -C 17 alkyl amidopropyl dimethyl carboxymethyl betaine.
  • Suitable cationic surfactants are inter alia the quaternary ammonium compounds of the formula (R vi )(R vii )(R viii )(R ix )N + X ⁇ , in which R vi to R ix denote four identical or different, in particular two long-chain and two short-chain, alkyl residues and X ⁇ denotes an anion, in particular a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride and mixtures thereof.
  • the agent contains are one or more anionic surfactants, preferably C 8 -C 18 alkyl sulfates and/or C 8 -C 18 alkyl ether sulfates, and/or one or more nonionic surfactants, preferably C 8-18 fatty alcohol polyglycol ethers with 2 to 8 EO and/or C 8-10 alkyl polyglucosides with 1 to 2 glycoside units.
  • anionic surfactants preferably C 8 -C 18 alkyl sulfates and/or C 8 -C 18 alkyl ether sulfates
  • nonionic surfactants preferably C 8-18 fatty alcohol polyglycol ethers with 2 to 8 EO and/or C 8-10 alkyl polyglucosides with 1 to 2 glycoside units.
  • the agents according to the invention contain at least one nonionic surfactant, which is/are in particular selected from ethoxylated and/or propoxylated alcohols with 8 to 18 C atoms in the alkyl moiety and 2 to 15 ethylene oxide (EO) and/or propylene oxide (PO) units and alkyl polyglycosides with 8 to 14 C atoms in the alkyl moiety and 1 to 3 glycoside units.
  • nonionic surfactant which is/are in particular selected from ethoxylated and/or propoxylated alcohols with 8 to 18 C atoms in the alkyl moiety and 2 to 15 ethylene oxide (EO) and/or propylene oxide (PO) units and alkyl polyglycosides with 8 to 14 C atoms in the alkyl moiety and 1 to 3 glycoside units.
  • the agents according to the invention preferably contain surfactants in quantities of 0.01 to 20 wt. %, in particular of 0.05 to 10 wt. %, preferably of 0.1 to 5 wt. % and particularly preferably of 0.2 to 1 wt. %, in each case relative to the total weight of the agent.
  • the agents according to the invention contain water and/or at least one nonaqueous solvent.
  • Nonaqueous solvents which may preferably be considered are those solvents which are water-miscible in any desired ratio.
  • the nonaqueous solvents include, for example, mono- or polyhydric alcohols, alkanolamines, glycol ethers and mixtures thereof.
  • the alcohols used are in particular ethanol, isopropanol and n-propanol.
  • Ether alcohols which may be considered are adequately water-soluble compounds with up to 10 C atoms per molecule.
  • ether alcohols examples include ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol mono-tert.-butyl ether and propylene glycol monoethyl ether, among which ethylene glycol monobutyl ether and propylene glycol monobutyl ether are in turn preferred.
  • ethanol is used as the nonaqueous solvent.
  • Nonaqueous solvents may be present in the agents according to the invention in quantities of 0.01 to 99.9 wt. %, in particular of 0.1 to 50 wt. %, and particularly preferably of 2 to 20 wt. %, in each case relative to the total weight of the agent.
  • Water is present in the agents according to the invention in quantities of 1 to 98 wt. %, in particular of 50 to 95 wt. %, and particularly preferably of 80 to 93 wt. %, in each case relative to the total weight of the agent.
  • the agent according to the invention contains a thickener.
  • a thickener any viscosity regulators used in the prior art in washing and cleaning agents may in principle be considered for this purpose, such as for example organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, guar gum, gellan gum, xanthan gum, alginates, pectins, polyoses, guar flour, locust bean flour, starch, dextrins, gelatin, casein), modified organic natural substances (carboxymethylcellulose and other cellulose ethers, hydroxyethylcellulose and hydroxypropylcellulose and the like, seed flour ethers as well as further derivatives of polysaccharides and heteropolysaccharides), completely synthetic organic thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides) and inorganic thickeners (polysilicic acids, clay minerals such as
  • the agent according to the invention contains a thickener
  • the latter is generally present in quantities of 0.01 to 30 wt. %, in particular of 0.2 to 15 wt. %.
  • the viscosity of the agents according to the invention may be adjusted within a wide range. Accordingly, low viscosity, virtually watery formulations may be preferred for multipurpose and bathroom cleaners, while higher viscosity, thickened formulations may be preferred for other applications, for example cleaning agents.
  • the viscosity of the agents according to the invention is in the range from 1 to 3,000 mPa ⁇ s, preferably from 200 to 1,500 mPa ⁇ s and particularly preferably from 400 to 900 mPa ⁇ s (Brookfield Rotovisco LV-DV II plus viscometer, spindle 31, 20° C., 20 rpm).
  • the agent according to the invention has a pH value of less than 9, in particular a pH value of 0 to 6, preferably of 1 to 5 and particularly preferably of 2 to 4.
  • the agent according to the invention contains at least one acid.
  • Suitable acids are in particular organic acids such as formic acid, acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or also amidosulfonic acid. It may, however, be preferred for acetic acid not to be used as the acid.
  • the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid or mixtures thereof may, however, additionally be used.
  • Particularly preferred acids are those selected from the group comprising amidosulfonic acid, citric acid, lactic acid and formic acid. They are preferably used in quantities of 0.01 to 30 wt. %, particularly preferably of 0.2 to 15 wt. %, in each case relative to the total weight of the agent.
  • the agents according to the invention may furthermore contain other conventional components of agents, in particular cleaning agents, for treating hard surfaces, provided that these do not interact in undesired manner with the substances used according to the invention.
  • agents which may for example be considered are further acids, salts, film formers, antimicrobial active ingredients, builders, corrosion inhibitors, complexing agents, sequestering agents, electrolytes, foam inhibitors, disintegration auxiliaries, soil-release active ingredients or soil-repellents, UV absorbers, alkalis, preservatives, bleaching agents, bleach activators, bleach catalysts, enzymes, enzyme stabilizers, abrasives, polymers together with fragrances and dyes.
  • the agents should preferably contain no more than 30 wt. %, preferably 0.01 to 30 wt. %, in particular 0.2 to 15 wt. % of further ingredients.
  • the agents according to the invention may contain film formers which may assist in improving wetting of surfaces.
  • film formers which may assist in improving wetting of surfaces.
  • Any film-forming polymers used in the prior art in laundry detergents and cleaning agents may in principle be considered for this purpose.
  • the film former is selected from the group comprising polyethylene glycol, polyethylene glycol derivatives and mixtures thereof, preferably with a molecular weight of between 200 and 20,000,000, particularly preferably of between 5,000 and 200,000.
  • the film former is advantageously used in quantities of 0.01 to 30 wt. %, in particular of 0.2 to 15 wt. %.
  • Agents according to the invention may furthermore contain one or more antimicrobial active ingredients, preferably in a quantity of 0.01 to 1 wt. %, in particular of 0.05 to 0.5 wt. %, particularly preferably of 0.1 to 0.3 wt. %.
  • Suitable antimicrobial active ingredients are for example those from the groups of alcohols, aldehydes, antimicrobial acids or the salts thereof, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenyl alkanes, urea derivatives, oxygen or nitrogen acetals and formals, benzamidines, isothiazoles and the derivatives thereof such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl butylcarbamate, iodine, iodophores and peroxides. It is furthermore also possible to use antimicrobially active essential oils which simultaneously fragrance the cleaning agent.
  • Water-soluble and/or water-insoluble builders may be used in the agents according to the invention.
  • Water-soluble builders are here preferred as they generally have a lesser tendency to leave insoluble residues behind on hard surfaces.
  • Conventional builders which may be present for the purposes of the invention are low molecular weight polycarboxylic acids and the salts thereof, homopolyrneric and copolymeric polycarboxylic acids and the salts thereof, citric acid and the salts thereof, carbonates, phosphates and silicates.
  • Water-insoluble builders include zeolites, which may likewise be used, together with mixtures of the above-stated builder substances. Reference is made to published patent application WO 2008/101909 with regard to further builders and/or cobuilders usable according to the invention and the preferred quantities thereof to be used.
  • Suitable corrosion inhibitors are for example the following substances listed by their INCI names: Cyclohexylamine, Diammonium Phosphate, Dilithium Oxalate, Dimethylamino Methylpropanol, Dipotassium Oxalate, Dipotassium Phosphate, Disodium Phosphate, Disodium Pyrophosphate, Disodium Tetrapropenyl Succinate, Hexoxyethyl Diethylammonium, Phosphate, Nitromethane, Potassium Silicate, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrite, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine. Reference is made to published patent application WO 2008/101909 with regard to further corrosion inhibitors, in particular also
  • Complexing agents which are also known as sequestrants, are ingredients which are capable of complexing and inactivating metal ions in order to prevent their disadvantageous effects on the stability or appearance, for example cloudiness, of the agents. On the one hand, it is important to complex the calcium and magnesium ions of water hardness which are incompatible with numerous ingredients. On the other hand, complexation of heavy metal ions such as iron or copper delays oxidative decomposition of the finished agents. Complexing agents additionally support the cleaning action.
  • the following complexing agents are for example suitable: Aminotrimethylene, Phosphonic Acid, Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactaric Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pent
  • Agents according to the invention may furthermore contain alkalis.
  • the bases used in agents according to the invention are preferably those from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide. It is, however, also possible additionally to use ammonia and/or alkanolamines with up to 9 C atoms per molecule, preferably ethanolamines, in particular monoethanolamine.
  • Agents according to the invention may likewise contain preservatives.
  • the substances stated in relation to the antimicrobial active ingredients may essentially be used for this purpose.
  • the agents may furthermore contain bleaching agents.
  • Suitable bleaching agents comprise peroxides, peracids and/or perborates; hydrogen peroxide is particularly preferred.
  • Sodium hypochlorite is less suitable in cleaning agents with an acidic formulation due to the release of toxic chlorine gas vapors, but may be used in alkaline cleaning agents.
  • a bleach activator may be present in addition to the bleaching agent.
  • the agent according to the invention may also contain enzymes, preferably proteases, lipases, amylases, hydrolases and/or cellulases. They may be added to the agent in any form established in the prior art. In the case of agents in liquid or gel form, this in particular includes solutions of the enzymes, advantageously as concentrated as possible, with a low water content and/or combined with stabilizers.
  • enzymes preferably proteases, lipases, amylases, hydrolases and/or cellulases.
  • the enzymes may be encapsulated, for example by spray drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer which is impermeable to water, air and/or chemicals.
  • Further active ingredients for example stabilizers, emulsifiers, pigments, bleaching agents or dyes may additionally be applied in superimposed layers.
  • Such capsules are applied in accordance with per se known methods, for example by agitated or rolling granulation or in fluidized bed processes.
  • such granules are low-dusting, for example due to the application of polymeric film formers, and stable in storage thanks to the coating.
  • Agents containing enzymes may furthermore contain enzyme stabilizers in order to protect an enzyme present in an agent according to the invention from damage, such as for example inactivation, denaturation or disintegration, for instance due to physical influences, oxidation or proteolytic cleavage.
  • suitable enzyme stabilizers are in particular: benzamidine hydrochloride, borax, boric acids, boronic acids or the salts or esters thereof, above all derivatives with aromatic groups, for instance substituted phenylboronic acids or the salts or esters thereof; peptide aldehydes (oligopeptides with a reduced C terminus), aminoalcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids or salts of the stated acids; end group-terminated fatty acid amide alkoxylates; lower aliphatic alcohols and especially polyols, for example glycerol, ethylene glycol, propylene glycol or sorbitol; and reducing agents and antioxidants such as sodium sulfite and reducing sugars.
  • benzamidine hydrochloride borax, boric acids, boronic acids or the salts or
  • stabilizers are known from the prior art.
  • Combinations of stabilizers are preferably used, for example the combination of polyols, boric acid and/or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
  • the agent according to the invention may finally contain one or more fragrances and/or one or more dyes as further ingredients.
  • Dyes which may be used are both water-soluble and oil-soluble dyes, it being necessary on the one hand to ensure compatibility with further constituents, for example bleaching agents, and, on the other hand, that the dye used should not have a substantive action towards the surfaces, in particular towards toilet ceramics, even in the event of an extended period of action. Selection of a suitable scent is likewise limited only by possible interactions with the other components of the cleaning agent.
  • a cleaning product for hard surfaces according to the invention may also contain one or more propellants (INCI Propellants), conventionally in a quantity of 1 to 80 wt. %, preferably of 1.5 to 30 wt. %, in particular of 2 to 10 wt. %, particularly preferably of 2.5 to 8 wt. %, extremely preferably of 3 to 6 wt. %.
  • one or more propellants ICI Propellants
  • the present invention also provides a product containing a cleaning product for hard surfaces according to the invention and a spray dispenser.
  • the product may here be both a single chamber and a multichamber container, in particular a two-chamber container.
  • the spray dispenser is here preferably a manually actuated spray dispenser, in particular selected from the group encompassing aerosol spray dispensers (pressurized gas container; also inter alia known as a spray can), self-pressurizing spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump spray dispensers and trigger spray dispensers with a container made from transparent polyethylene or polyethylene terephthalate.
  • Spray dispensers are described in greater detail in WO 96/04940 (Procter & Gamble) and the US patents cited therein in relation to spray dispensers, to which full reference is made in this respect and the content of which is hereby incorporated into the present application.
  • Trigger spray dispensers and pump atomizers have the advantage over pressurized gas containers that no propellant need be used.
  • Suitable attachments, nozzles etc. (“nozzle-valves”) on the spray dispenser through which particles can pass mean that an optionally present enzyme may in this embodiment optionally also be added to the agent in a form immobilized on particles and accordingly be dispensed as a cleaning foam.
  • the agent according to the invention is preferably a cleaning agent, in particular a cleaning agent for ceramics, particularly preferably for ceramic sanitary ware.
  • the agent according to the invention may be produced in a manner conventional in the art by suitably mixing the components present in the agent with one another.
  • the present invention accordingly also provides a method for producing an agent according to the invention, in which the individual components are mixed with one another.
  • the present invention also provides a method for treating a hard surface, in which the surface is brought into contact with an agent according to the invention, as described in the preceding text.
  • This method may be carried out as an independent treatment method for the surface, for example in order to provide it with dirt-repellent properties or one or more of the other properties brought about by the agents according to the invention in accordance with the teaching of the present invention.
  • the surface is here brought into contact with an agent according to the invention.
  • the method according to the invention is preferably carried out in such a manner that the agent is distributed over the surface and advantageously then either rinsed off after a period of action of 1 second to 20 minutes, preferably of 1 to 10 minutes, or alternatively left to dry.
  • contacting proceeds at a temperature of 5 to 50° C., in particular of 15 to 35° C.
  • the method according to the invention is a cleaning method which serves for surface cleaning.
  • the method according to the invention serves for treating a surface of ceramics, glass, stainless steel or plastics material.
  • Another embodiment of the invention relates to the use of an agent according to the invention for protecting a hard surface from soiling and/or for easier detachment of renewed soiling from the surface, the soiling in particular involving fecal soiling and/or biofilms and/or protein deposits.
  • agents according to the invention serve for the improved removal of fecal soiling and/or biofilms from the surfaces of flush toilets and/or for reducing renewed soiling of such surfaces with fecal soiling and/or biofilms.
  • the agent is advantageously distributed over the surface and either rinsed off after a period of action of preferably 1 to 10 minutes or alternatively left to dry. Once the surface has been treated in this manner, fecal soiling is easier to remove, often without the assistance of mechanical aids, such as for instance a toilet brush. Any dried on cleaning agent residues may additionally be rinsed away more easily.
  • Another embodiment of the invention relates to the use of an agent according to the invention for providing a water-repellent finish on a hard surface and/or for shortening the drying time of a hard surface after exposure to water.
  • treating a surface with the agents according to the invention renders this surface hydrophilic. These facilitates wetting and detachment of dirt and simultaneously ensures that the surface is readily “dewetted” of a film of water, so avoiding water drops being formed and residual soiling being left behind.
  • This property is particularly beneficial where surfaces are particularly exposed to lime and dirt and biofilm deposits, such as typically toilet bowls, washbasins, bathtubs and shower cubicles.
  • Another advantage of this property is that water drains away faster from treated surfaces and these consequently dry more quickly.
  • rinsing with clean water is generally required after treating the surface with cleaning product. It is desirable for the surfaces to dry quickly after this rinsing, for example because a quickly drying surface enhances the consumer's impression of cleanliness.
  • the present invention also provides the use of an agent according to the invention for providing a bacteriostatic finish on a hard surface.
  • One particular advantage of the polymer mixtures used according to the invention is that colonization by and the growth of microorganisms is suppressed on surfaces treated therewith, without biocides being required for this purpose. In this manner, a surface finish is obtained on which bacterial multiplication is prevented or substantially delayed. This is a distinct advantage relative to the prior art, in particular in the light of the fact that the use of biocides is regarded increasingly more critically with regard to environmental and consumer protection.
  • Another embodiment of the invention accordingly relates to the use of polymer mixtures according to the invention for providing a bacteriostatic finish on a hard surface.
  • Bathroom cleaners which are particularly preferred according to the invention comprise:
  • Toilet cleaners which are particularly preferred according to the invention comprise:
  • Multipurpose cleaners which are particularly preferred according to the invention comprise:
  • % of an organic solvent in particular ethanol; and (d) 0.01 to 5 wt. %, preferably 0.02 to 4 wt. % and in particular 0.05 to 3 wt. % of at least two polymers selected from the group consisting of a multi-armed polyalkoxylate, in particular silyl polyalkoxylate, a polyesteramide and a copolymer prepared from a quaternary ammonium acrylamide and acrylic acid; wherein the cleaners have a pH value of 8 to 12, preferably of 9 to 11.
  • the starting material used was polyether polyol which is a hexa-armed random poly(ethylene oxide-co-propylene oxide) with an EO:PO ratio of 80:20 and with a molecular weight of 12,000 g/mol and was produced by anionic ring-opening polymerization of ethylene oxide and propylene oxide using sorbitol as initiator. Before being further reacted, the polyether polyol was heated to 80° C. for 1 h under a vacuum with stirring.
  • the product comprising in each case a triethoxylsilyl group at the free ends of the polymer arms of the stellate prepolymer, was obtained as a colorless viscous liquid.
  • IR film, cm ⁇ 1 ): 3349 (m, —CO—NH—), 2868 (s, —CH 2 —, —CH 3 ), 1719 (s, —C ⁇ O), 1456 (m, —CH 2 —, —CH 3 ), 1107 (s, —C—O—C—), 954 (m, —Si—O—).
  • Voranol CP 1421 from DOW Chemicals was dried for 1 h at 80° C. under a vacuum with stirring. 317 mg (1.0 equivalent) of (3-isocyanatopropyl)triethoxysilane were slowly added to 2.04 g (0.41 mmol) of the dried polyether polyol. The reaction mixture was stirred under protective gas at 100° C. for a further 2 days, until the NCO group vibration band on IR measurement had disappeared. The product, comprising in each case a triethoxylsilyl group at the free ends of the polymer arms of the polyether polyol, was obtained as a colorless viscous liquid.
  • Voranol 4053 from DOW Chemicals was dried for 1 h at 80° C. under a vacuum with stirring. 20.9 mg (0.01%) of dibutyltin dilaurate and 30.3 g (1.0 equivalent) of (3-isocyanatopropyl)triethoxysilane were slowly added to 209 g (16.9 mmol) of the dried polyether polyol.
  • dibutyltin dilaurate DABCO (1,4-diazabicyclo[2.2.2]octane) may for instance also be used as catalyst.
  • the reaction mixture was stirred under protective gas at room temperature for a further 2 days, until the NCO band on IR measurement had disappeared.
  • the product comprising in each case a triethoxylsilyl group at the free ends of the polymer arms of the polyether polyol and constituting a mixture of a tri-armed and an octa-aimed polyalkoxylate in a ratio of approx. 20:80, was obtained as a colorless viscous liquid (Hydrostellan S100).
  • the “toilet reactor” replicates the flushing cycles of a toilet and thus the periodic wetting and drying of ceramic surfaces.
  • This system makes it possible to investigate adhesion and biofilm formation in a test system on several different surfaces over a defined period of 48 h. Instead of the water used in a real toilet, it is fresh medium (TBY 1:50) which is passed over the glazed tiles.
  • the reactor is initially filled with 680 ml of medium and inoculated with a microbial mixture consisting of Dermacoccus nishinomiyaensis DSMZ 20448, Bradyrhizobium japonicum DSMZ 1982 and Xanthomonas campestris DSMZ 1526, which forms a stable biofilm in aqueous environments. Incubation proceeds overnight, so that the microbial flora can get established in the system.
  • a microbial mixture consisting of Dermacoccus nishinomiyaensis DSMZ 20448, Bradyrhizobium japonicum DSMZ 1982 and Xanthomonas campestris DSMZ 1526, which forms a stable biofilm in aqueous environments. Incubation proceeds overnight, so that the microbial flora can get established in the system.
  • Water flushing proceeds under semi-automatic control by a pump and the time-delayed opening of a solenoid valve. 680 ml of medium are used per flush. On each of the first and second days after incubation, flushing is performed 15 times, an individual flush cycle lasting for 20 minutes.
  • the glazed tiles are removed at the end of the reactor run.
  • the horizontally placed glazed tiles were immersed for three minutes in 15-20 ml of the polymer solution at defined concentrations, then briefly rinsed with water and dried for two hours at 60° C.
  • a cleaning product formulation was used as solvent.
  • the glazed ceramic tiles were dried at room temperature and then each stained with 6 ml of 0.01% Safranin O solution for 15 minutes. The stain solution is then drawn off, any unbound stain is removed from the tiles with twice-distilled H 2 O and the stained glazed tiles are dried. The stained surfaces are scanned and evaluated with Corel Draw Paint 9. The background value (caused by the ceramic) is measured on untreated surfaces and deducted from the detected color intensity of the stained glazed tiles. The intensity of the biofilm on glazed tiles which were treated at the outset solely with the cleaning product without added polymer is set as the reference value for 100% biofilm formation or 0% biofilm reduction.
  • DSM Hybrane DAEO 5000 is a branched polyesteramide which contains quaternized ammonium groups and long-chain polyoxyethylene groups.
  • biocidal properties of the individual polymers were investigated to standard DIN-EN 1276 on Staphylococcus aureus, Enterococcus hirae, Pseudomonas aeruginosa and Escherichia coli.
  • biocidal properties were then compared with the biorepulsive properties of the polymers, which were determined as described in Example 2.
  • Glazed tiles which were treated at the outset with water, were used as the reference in order to ascertain biofilm reduction by the toilet cleaner itself.
  • the toilet cleaner with addition of the polymers Hydrostellan, DSM Hybrane Quat or DSM Hybrane 5000 in each case exhibited an approx. 70% increase in biofilm reduction.
  • the biocidal action of the various cleaning product formulations was very largely maintained. Both the 80% cleaning product/polymer formulations under ‘clean’ and ‘dirty’ conditions, and the 10% formulations under ‘clean’ conditions, exhibited the same biocidal action as the toilet cleaner without polymer.
  • the values in the table are stated in wt. % active substance relative to the total composition.
  • the pH value of the compositions was adjusted to 2.2.
  • the viscosity of the compositions at 20° C. was 550 mPa ⁇ s (Brookfield LV-DV II+, spindle 31, 20 rpm).
  • the values in the table are stated in wt. % active substance relative to the total composition.
  • the pH value of the compositions was adjusted to 3.9.
  • the viscosity of the compositions at 20° C. was less than 10 mPa ⁇ s (Brookfield LV-DV II+, spindle 31, 20 rpm).

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US13/409,354 2009-09-01 2012-03-01 Agent for treating hard surfaces Abandoned US20120156377A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102009029060.5 2009-09-01
DE102009029060A DE102009029060A1 (de) 2009-09-01 2009-09-01 Mittel zur Behandlung harter Oberflächen
PCT/EP2010/062108 WO2011026735A1 (de) 2009-09-01 2010-08-19 Mittel zur behandlung harter oberflächen

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JP2021172715A (ja) * 2020-04-23 2021-11-01 山崎産業株式会社 防汚洗浄剤、清掃用品及び防汚洗浄方法
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Publication number Priority date Publication date Assignee Title
US20110033702A1 (en) * 2007-09-06 2011-02-10 Saint-Gobain Technical Fabrics Europe Sizing composition in the form of a physical gel for glass strands, glass strands obtained and composites comprising the said strands
US8999505B2 (en) * 2007-09-06 2015-04-07 Saint-Gobain Adfors Sizing composition in the form of a physical gel for glass strands, glass strands obtained and composites comprising the said strands
US20150126429A1 (en) * 2012-04-25 2015-05-07 Akzo Nobel Chemicals International B.V. Use Of An Ethoxylated Alkanolamide As A Hydrotrope For An Alkylene Oxide Adduct Of An Alcohol
US20140174467A1 (en) * 2012-12-20 2014-06-26 Ecolab Usa Inc. Citrate salt bathroom cleaners
US20140174480A1 (en) * 2012-12-20 2014-06-26 Ecolab Usa Inc. Citrate salt bathroom cleaners
US9834742B2 (en) 2012-12-20 2017-12-05 Ecolab Usa Inc. Citrate salt bathroom cleaners
US9534190B2 (en) * 2012-12-20 2017-01-03 Ecolab Usa Inc. Citrate salt bathroom cleaners
US9790456B2 (en) * 2012-12-20 2017-10-17 Ecolab Usa Inc. Citrate salt bathroom cleaners
US20170158989A1 (en) * 2014-02-11 2017-06-08 Gregory E. Robinson Multi-Purpose Cleaner
US9611449B2 (en) * 2014-02-11 2017-04-04 Gregory E Robinson Multi-purpose cleaning composition
US20150225671A1 (en) * 2014-02-11 2015-08-13 Gregory E. Robinson Multi-Purpose Cleaning Composition
US10093886B2 (en) * 2014-02-11 2018-10-09 Gregory E. Robinson Multi-purpose cleaner
US20170181436A1 (en) * 2014-04-15 2017-06-29 Bmb Gebäudehygiene Gmbh Method of fighting surface microorganisms
US10548323B2 (en) * 2014-04-15 2020-02-04 Bmb Gebaeudehygiene Gmbh Method of fighting surface microorganisms
US20180030389A1 (en) * 2016-07-29 2018-02-01 Amit Garyali Multi-Purpose Cleaner System
US11591548B2 (en) * 2017-12-19 2023-02-28 Colgate-Palmolive Company Cleaning composition to provide long-lasting water repellency on surfaces
JP2021172715A (ja) * 2020-04-23 2021-11-01 山崎産業株式会社 防汚洗浄剤、清掃用品及び防汚洗浄方法
WO2024028618A1 (en) * 2022-08-01 2024-02-08 Papadopoulos Nikolaos-Xafakis Sotirios G.P. Anti-soiling nano-coating systems with enhanced antimicrobial activity

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DE102009029060A1 (de) 2011-03-03
WO2011026735A1 (de) 2011-03-10
ES2618862T3 (es) 2017-06-22
EP2473592B1 (de) 2016-12-21
EP2473592A1 (de) 2012-07-11
PL2473592T3 (pl) 2017-06-30

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